Process for producing toluene sulphonamid-aldehyde resins



Patented May 9, 1933 UNITED "STATES PATENT OFFICE wnmmu HENRY MOSS ANDamncnn a. warm, or eummamnny mum,

nssrenoss ro onnannsn'oonronarron or names, A. conronyrron or nm- WARErnocnss For. rnonuome 'ronumm sunrnorimrn-annnmuimms 80 Drawing.

This invention relates to the pre arationof a synthetic resin fromtoluene s phonannd, an also to coating. or plastic composltlonscontaining derivatlves of cellulose, and particularl organic derivativesof cellulose.

An ject of our invention is to prepare a synthetic resinthat iscompatible with derivatives of cellulose, and therefore suitable for usein the films, lacquersor other coating compositions or plasticscontaining such derivatives of cellulose.

A further object of our invention is to prepare a toluene sulphonamidresin, which is harder than toluene sulphonamid resins reviously made,and which is free from de e'cts occurring in suchrior resins.

\Other objects 0 our invention will appeanin the following detaileddescription: 7.

While a resin has beenpreviously prepared by the condensation ofpara-toluene .sulphonamid .and formaldehyde, this resin,

is very soft. Therefore, when it is used in coating or plasticcompositions containing cellulose esters, it acts more as a lastifierproduce soft films or articles an as a resin, since it doesnot impartgloss, adhesion or hardness to a film containing the'same as isfi'equired of a resin when used in lacquer.

Furthermore, the soft resins previously prepared contain a large amountof unconverted toluene sulphonamid, and solutions of these, resins,decompose spontaneously to produce more free toluene sulphonamid.-

' This free toluene sul honamid is an unde- 'sirable com onent in fi s,arns orplastics containing erivatives of ce ulose, as it tends toseparate out, as is indicated by the fact thatcfilms or lasticscontaining-. esters -of 4 cellulose and t e toluene sulphonamid resin inamounts of say% to 200% of the.

wei ht of the-cellulose ester, show a tendency to loom-.in-sunlight,which bloom is due to .a fine:;-erystalline appearance on the surface ofthe film or plastic, because ofthe separation of the toluene's'ulphonamid.

A further objection to thepresence of the v free toluene sulphonamid isdue to the fact that a water solution thereof has an acid reaction. Thedecomposition of the prior toluene sulphonamia IGSlllgiS shown by thefact ing the solution Applicationfiled August. 1a, 1928. Serial No.300,154. n

that a solution of the resin in benzene, which solution has beenpreviouslyfiltered to re.- move insolublematter, deposits onstandin alarge quantity. of free toluene sulphonami which is onlyslightly'soluble in benzene..

We have found that if toluene sulphonamid is condensed withequimolecular proportions of formaldehyde or otheraldeh de or othercompound having a reactive met ylene roup in the presence or absence ofurea, and t e resulting resin is heated first to remove the waterpresent and then under reflux a hard toluene sulphonamid resin isproduced, which is soluble in man solvents, is compatible withderivatives 0 cellulose such'fas cellulose acetate, is free of and doesnot decompose to form toluene sulphonamid, and which may films,containing derivatives of cellulose.

I The resin formed in accordance with'our invention, may be employed inmaking so- 1 lutions, coating or plastic compositions con-- tainingderivatives of cellulose and a suitable solvent. I

These solutions or compositions ma contain suitable low, medium and/orhigli boiling solvents, lasticizers or softening agents other resins,0th natural or synthetic and pigments or dyes. 0 T

The solutions thus formed, may be 'employedas lacquer-or coatingcompositions for metallic, glass or other surfaces and ma. be used formaking photographic or other Artificial yarns may-be formed byextrudsheets to adhere to surfaces of sheets of glass between which theyare placed. The plastic containing our resin, may be for laminatedglass, and also may be worked into-blocks or articlesin any. knownmanner.

The derivatives of cellulose that may be- I used for making solutionscoating or plastic th?u%h the-orifices'ofaspinnerette, either mt a eatedevaporative at.-

Worked into sheets, which may also-be used The low boiling solvent thatmay be emuct, having a melting.

- heated under reflux at 150 twentyhours and preferably in a jacketed-GH3-G6H4SO2N are heated together.

such as para-formaldehyde.

ployed may be one or a mixture of two or more of the following: acetone,alcohol, benzene or ethylene dichloride. Examples of medium and/or highboiling solvents, are ethyl acetate, ethyl lactate, tetrachlorethane,benzyl alcohol or .diacetone alcohol. Examples of suitable plasticizersare diphenylol propane, monomethyl xylene sulphonamid, ortho or metaethyl toluene sulphonamid. If desired, fire retardants may be added,particularly the very effective bromine derivatives of organiccompounds, such as brominated tricresyl phosphate.

Thepigments or' dyes that may be used are any of'the ordmarypigments ordyes used in the paint or lacquer industry.

Of the-naturalgums or resins that-may be employed, the following may bementioned:

Manila, accaroides, pontianak, kaui'i, dammar, rosin and -shellac. Thesemi-synthetic resin,ester gumwhich is the glycerol ester ofrosm,'mayalso-be added. Examples of other synthetic resins that mag be used inconjunction' with our resin, aret e fusible and solublephenol-formaldehyde, diphenylol ropaneformaldehyde and phenol-furfuraresins, preferably prepared in'the presence of acid catalysts. j I

The following is a detailed descri' tion of one mode of prepar' ourresin: E qui-molecular proportions 0 am toluene sulphona} andformaldehyde, The. toluene sulphonamid that is employed may be thevpureprodpoint of 1371C or it may be-a commercial melting point. -Theformaldehyde may be employe in the form of a 40% aqueous solution, or inthe form of one of its polymers,

While equi-molecular proportions of the reactants are preferred, theproportions used may be varied considerably. The mixture of thereactants is C. forsixteen to vessel having oil or other heating mediumin the jacket. The condensation may be caused to take place in thepresence of an acid or alkaline catalyst, but the presence of catalystis not necessary. The product thus formed, is a soft yellow resin.- 'Itmay be washed with water to remove any excess of formaldehyde or toluenesulphonamid present, and the water then removed by heating or otherwise.

In order to. prepare the harder and improved resin, the product of thereaction at product, having a l6werloosely combine-d formaldehyde firstsplits oil from the resin and then recombines on be ing returned fromthe reflux condenser. It that this heatingis particularly necessarshould be done under re uX, since-1f the heating 1s done in anopen'vessel, the resin Wlll char, froth up and be cnverted to a blacksemi-crystalline mass in a short time. At this state of the heating,excess para formaldehyde may be added in amounts up to 15 or 20% of onemolecular proportion based on the amount of p-toluene sulphonamidoriginally used.

This heating is continued from 15 minutes to three hours or thereabouts.time, the resin is distilled at ordinary pressure at 100-150 C. for15'minutes to 1 hour. The product thus obtained is a clear, light yellowresin, having a melting point of 3540 It is entirely soluble 'inacetone, alcohol and in benzene, and the solutions in benzene do notdeposit any free toluene sulphonamid. It is completely compatible in allproportions with cellulose acetate threads, lacquers etc., made from it,show no tendency to bloom on the surface.

In.another mode of carrying. out our invention, an improved non-bloomingresin is prepared by adding a small proportionof At the end of thisandfilms, plastics,

sists of a layer of resin and one of water.

brown resin thus formed is soluble in acetone, alcohol and benzene andis suitable for admixture with cellulose acetate and other cellulosederivatives to produce films, plastics, etc., which do not bloom. Owingto thecomplete compatibility with cellulose acetate, the resin isparticularly suited foradmixture with it in any of the numeroustechnical applications of this ester. It may be used in small pro- 4portions to give films which have greater tensile strength thanfilms'from the cellulose ester alone. Such films are suitable for photography or protective coating on cloth, fab

It may be added .td; cellulose esters in the'production therefrord ric,wire, leather,- etc.

offilamentsand threads, as in the manufaeture of artificial silk. Inlarger proportions, it is especially useful in cellulose acetate "Thewatery layer isdecanted or' distilled off quers, plastics and solutionsfor use as adhesive.

It is to be understood that the foregoing detailed description is givenmerely by way of illustration, and that many variations may-be madetherein, without departing from the spirit of our invention. Havingdescribed our invention,'w hat we claim and desire to secure by LettersPatcut is: Y

v 1. In the methodof preparing a' synthetic resin, the step ofheating-toluene sulphonamid and an aldehyde,-in the presence of a smallproportion of urea; t 2. In the method of preparing a synthetic resin,the step of heating toluene sulphonamid and formaldehyde in the presenceof a small proportion of urea. V

3. Method ofprep'aring a synthetic resin comprising heatin toluenevsulphonamid and an aldehyde un er reflux until condensationtakes place,separating the reaction plrodnot and heating toremove excess water,eating at a temperature substantiall between 200 and 260 C. underreflux, and pally distilling at ordinary pressure at substantially 100to 150C. 1

4. Method :of preparing a synthetic resin 7 comprising heating toluenesulphonamid and to formaldehyde under reflux until condensation takesplace, separating the reaction roduct and heating to remove excesswater, eat ing at a temperature substantiall between 200 and 260 C.under reflux,.and finally didtilling at ordinary pressure atsubstantially 100to150C.'

- In testimony whereof, we have hereunto subscribed our names. 4 WILLIAMHENRY MOSS. 4o BLANOHE B. WHITE.

